Coupled atmospheric chemistry, radiation, and dynamics of an exoplanet generate self-sustained oscillations.

Nonlinearity in photochemical systems is known to allow self-sustained oscillations, but they have received little attention in studies of planetary atmospheres. Here, we present a unique, self-oscillatory solution for ozone chemistry of an exoplanet from a numerical simulation using a fully coupled, three-dimensional (3D) atmospheric chemistry-radiation-dynamics model. Forced with nonvarying stellar insolation and emission flux of nitric oxide (NO), atmospheric ozone abundance oscillates by a factor of thirty over a multidecadal timescale. As such self-oscillations can only occur with biological nitrogen fixation contributing to NO emission, we propose that they are a unique class of biosignature. The resulting temporal variability in the atmospheric spectrum is potentially observable. Our results underscore the importance of revisiting the spectra of exoplanets over multidecadal timescales to characterizing the atmospheric chemistry of exoplanets and searching for exoplanet biosignatures. There are also profound implications for comparative planetology and the evolution of the atmospheres of terrestrial planets in the solar system and beyond. Fully coupled, 3D atmospheric chemistry-radiation-dynamics models can reveal new phenomena that may not exist in one-dimensional models, and hence, they are powerful tools for future planetary atmospheric research.

Decadal decrease in Los Angeles methane emissions is much smaller than bottom-up estimates.

Methane, a powerful greenhouse gas, has a short atmospheric lifetime ( ~ 12 years), so that emissions reductions will have a rapid impact on climate forcing. In megacities such as Los Angeles (LA), natural gas (NG) leakage is the primary atmospheric methane source. The magnitudes and trends of fugitive NG emissions are largely unknown and need to be quantified to verify compliance with emission reduction targets. Here we use atmospheric remote sensing data to show that, in contrast to the observed global increase in methane emissions, LA area emissions decreased during 2011-2020 at a mean rate of (-1.57 ± 0.41) %/yr. However, the NG utility calculations indicate a much larger negative emissions trend of -5.8 %/yr. The large difference between top-down and bottom-up trends reflects the uncertainties in estimating the achieved emissions reductions. Actions taken in LA can be a blueprint for COP28 and future efforts to reduce methane emissions.

Evaluation of Modeled Hyperspectral Infrared Spectra Against All-Sky AIRS Observations Using Different Cloud Overlap Schemes.

Hyperspectral infrared sounding contains information about clouds, which plays an important role in modulating Earth's climate. However, there is a great deal of uncertainty in modeling the radiative effect of clouds due to its complex dependence on various parameters. Therefore, cloudy scenarios are often neglected in retrievals of infrared spectral measurements and in data assimilation. One-dimensional radiative transfer (RT) models have a limited capability to represent the cloud three-dimensional multilayer structure. This issue is typically resolved by using a multiple independent column approach, which is computationally demanding. Therefore, it is necessary to find a balance between computational speed and accuracy for infrared RT all-sky radiance simulations. In this study, we utilize the Community Radiative Transfer Model with four different cloud overlap schemes and compare against observations made by the Atmospheric Infrared Sounder (AIRS) using a statistical metric called the first Wasserstein distance. Our results show that the average cloud overlap scheme performs the best and successfully predicts the overall probability distribution of brightness temperature over nonfrozen oceans for a wide range of wavelengths. The mean absolute differences are less than 0.7 K for 846 selected AIRS channels between 790 cm-1 and 1231 cm-1.

Seasonal Variations of Solar-Induced Fluorescence, Precipitation, and Carbon Dioxide Over the Amazon.

Previous studies suggested that the Amazon, the largest rainforest on Earth, changes from a CO2 sink to a CO2 source during the dry/fire season. However, the biospheric contributions to atmospheric CO2 are not well understood during the two main seasons, the dry/fire season and the wet season. In this article, we utilize Orbiting Carbon Observatory 2 (OCO-2) Solar-Induced Fluorescence (SIF) to explore photosynthetic activity during the different seasons. The spatiotemporal variability of OCO-2 SIF, OCO-2 CO2, precipitation, and burned area are investigated over the Amazon from September 2014 to December 2019. Averaging over the entire Amazon region, we found a positive temporal correlation (0.94) between OCO-2 SIF and Global Precipitation Climatology Project precipitation and a negative temporal correlation (-0.64) between OCO-2 SIF and OCO-2 CO2, consistent with the fact that precipitation enhances photosynthesis, which results in higher values for SIF and rate of removal of CO2 from the atmosphere above the Amazon region. We also observed seasonality in the spatial variability of these variables within the Amazon region. During the dry/fire (August-October) season, low SIF values, low precipitation, high vapor pressure deficit (VPD), large burned areas, and high atmospheric CO2 are mainly found over the southern Amazon region. In contrast, during the wet season (January-March), high SIF values, high precipitation, low VPD, smaller burned areas, and low CO2 are found over both the central and southern Amazon regions. The seasonal difference in SIF suggests that photosynthetic activity is reduced during the dry/fire season relative to the wet season as a result of low precipitation and high VPD, especially over the southern Amazon region, which will contribute to more CO2 in the atmosphere during the dry/fire season.

Computation by Convective Logic Gates and Thermal Communication.

We demonstrate a novel computational architecture based on fluid convection logic gates and heat flux-mediated information flows. Our previous work demonstrated that Boolean logic operations can be performed by thermally driven convection flows. In this work, we use numerical simulations to demonstrate a different , but universal Boolean logic operation (NOR), performed by simpler convective gates. The gates in the present work do not rely on obstacle flows or periodic boundary conditions, a significant improvement in terms of experimental realizability. Conductive heat transfer links can be used to connect the convective gates, and we demonstrate this with the example of binary half addition. These simulated circuits could be constructed in an experimental setting with modern, 2-dimensional fluidics equipment, such as a thin layer of fluid between acrylic plates. The presented approach thus introduces a new realm of unconventional, thermal fluid-based computation.

A bimodal distribution of haze in Pluto's atmosphere.

Pluto, Titan, and Triton make up a unique class of solar system bodies, with icy surfaces and chemically reducing atmospheres rich in organic photochemistry and haze formation. Hazes play important roles in these atmospheres, with physical and chemical processes highly dependent on particle sizes, but the haze size distribution in reducing atmospheres is currently poorly understood. Here we report observational evidence that Pluto's haze particles are bimodally distributed, which successfully reproduces the full phase scattering observations from New Horizons. Combined with previous simulations of Titan's haze, this result suggests that haze particles in reducing atmospheres undergo rapid shape change near pressure levels ~0.5 Pa and favors a photochemical rather than a dynamical origin for the formation of Titan's detached haze. It also demonstrates that both oxidizing and reducing atmospheres can produce multi-modal hazes, and encourages reanalysis of observations of hazes on Titan and Triton.

Quantifying Northern High Latitude Gross Primary Productivity (GPP) Using Carbonyl Sulfide (OCS).

The northern high latitude (NHL, 40°N to 90°N) is where the second peak region of gross primary productivity (GPP) other than the tropics. The summer NHL GPP is about 80% of the tropical peak, but both regions are still highly uncertain (Norton et al. 2019, https://doi.org/10.5194/bg-16-3069-2019). Carbonyl sulfide (OCS) provides an important proxy for photosynthetic carbon uptake. Here we optimize the OCS plant uptake fluxes across the NHL by fitting atmospheric concentration simulation with the GEOS-CHEM global transport model to the aircraft profiles acquired over Alaska during NASA's Carbon in Arctic Reservoirs Vulnerability Experiment (2012-2015). We use the empirical biome-specific linear relationship between OCS plant uptake flux and GPP to derive the six plant uptake OCS fluxes from different GPP data. Such GPP-based fluxes are used to drive the concentration simulations. We evaluate the simulations against the independent observations at two ground sites of Alaska. The optimized OCS fluxes suggest the NHL plant uptake OCS flux of -247 Gg S year-1, about 25% stronger than the ensemble mean of the six GPP-based OCS fluxes. GPP-based OCS fluxes systematically underestimate the peak growing season across the NHL, while a subset of models predict early start of season in Alaska, consistent with previous studies of net ecosystem exchange. The OCS optimized GPP of 34 PgC yr-1 for NHL is also about 25% more than the ensembles mean from six GPP data. Further work is needed to fully understand the environmental and biotic drivers and quantify their rate of photosynthetic carbon uptake in Arctic ecosystems.

Societal shifts due to COVID-19 reveal large-scale complexities and feedbacks between atmospheric chemistry and climate change.

The COVID-19 global pandemic and associated government lockdowns dramatically altered human activity, providing a window into how changes in individual behavior, enacted en masse, impact atmospheric composition. The resulting reductions in anthropogenic activity represent an unprecedented event that yields a glimpse into a future where emissions to the atmosphere are reduced. Furthermore, the abrupt reduction in emissions during the lockdown periods led to clearly observable changes in atmospheric composition, which provide direct insight into feedbacks between the Earth system and human activity. While air pollutants and greenhouse gases share many common anthropogenic sources, there is a sharp difference in the response of their atmospheric concentrations to COVID-19 emissions changes, due in large part to their different lifetimes. Here, we discuss several key takeaways from modeling and observational studies. First, despite dramatic declines in mobility and associated vehicular emissions, the atmospheric growth rates of greenhouse gases were not slowed, in part due to decreased ocean uptake of CO2 and a likely increase in CH4 lifetime from reduced NO x emissions. Second, the response of O3 to decreased NO x emissions showed significant spatial and temporal variability, due to differing chemical regimes around the world. Finally, the overall response of atmospheric composition to emissions changes is heavily modulated by factors including carbon-cycle feedbacks to CH4 and CO2, background pollutant levels, the timing and location of emissions changes, and climate feedbacks on air quality, such as wildfires and the ozone climate penalty.

From COVID-19 to future electrification: Assessing traffic impacts on air quality by a machine-learning model.

The large fluctuations in traffic during the COVID-19 pandemic provide an unparalleled opportunity to assess vehicle emission control efficacy. Here we develop a random-forest regression model, based on the large volume of real-time observational data during COVID-19, to predict surface-level NO2, O3, and fine particle concentration in the Los Angeles megacity. Our model exhibits high fidelity in reproducing pollutant concentrations in the Los Angeles Basin and identifies major factors controlling each species. During the strictest lockdown period, traffic reduction led to decreases in NO2 and particulate matter with aerodynamic diameters <2.5 µm by -30.1% and -17.5%, respectively, but a 5.7% increase in O3 Heavy-duty truck emissions contribute primarily to these variations. Future traffic-emission controls are estimated to impose similar effects as observed during the COVID-19 lockdown, but with smaller magnitude. Vehicular electrification will achieve further alleviation of NO2 levels.

Sulfur monoxide dimer chemistry as a possible source of polysulfur in the upper atmosphere of Venus.

The abundance of SO dimers (SO)2 in the upper atmosphere of Venus and their implications for the enigmatic ultraviolet absorption has been investigated in several studies over the past few years. However, the photochemistry of sulfur species in the upper atmosphere of Venus is still not well understood and the identity of the missing ultraviolet absorber(s) remains unknown. Here we update an existing photochemical model of Venus' upper atmosphere by including the photochemistry of SO dimers. Although the spectral absorption profile of SO dimers fits the unknown absorber, their abundance is found to be too low for them to contribute significantly to the absorption. It is more likely that their photolysis and/or reaction products could contribute more substantively. Reactions of SO dimers are found to be important sources of S2O, and possibly higher order SnO species and polysulfur, Sn. All of these species absorb in the critical ultraviolet region and are expected to be found in both the aerosol and gas phase. indicating that in-situ high resolution aerosol mass spectrometry might be a useful technique for identifying the ultraviolet absorber on Venus.

Quantifying Mineral-Ligand Structural Similarities: Bridging the Geological World of Minerals with the Biological World of Enzymes.

Metal compounds abundant on Early Earth are thought to play an important role in the origins of life. Certain iron-sulfur minerals for example, are proposed to have served as primitive metalloenzyme cofactors due to their ability to catalyze organic synthesis processes and facilitate electron transfer reactions. An inherent difficulty with studying the catalytic potential of many metal compounds is the wide range of data and parameters to consider when searching for individual minerals and ligands of interest. Detecting mineral-ligand pairs that are structurally analogous enables more relevant selections of data to study, since structural affinity is a key indicator of comparable catalytic function. However, current structure-oriented approaches tend to be subjective and localized, and do not quantify observations or compare them with other potential targets. Here, we present a mathematical approach that compares structural similarities between various minerals and ligands using molecular similarity metrics. We use an iterative substructure search in the crystal lattice, paired with benchmark structural similarity methods. This structural comparison may be considered as a first stage in a more advanced analysis tool that will include a range of chemical and physical factors when computing mineral-ligand similarity. This approach will seek relationships between the mineral and enzyme worlds, with applications to the origins of life, ecology, catalysis, and astrobiology.

Unexpected air pollution with marked emission reductions during the COVID-19 outbreak in China.

The absence of motor vehicle traffic and suspended manufacturing during the coronavirus disease 2019 (COVID-19) pandemic in China enabled assessment of the efficiency of air pollution mitigation. Up to 90% reduction of certain emissions during the city-lockdown period can be identified from satellite and ground-based observations. Unexpectedly, extreme particulate matter levels simultaneously occurred in northern China. Our synergistic observation analyses and model simulations show that anomalously high humidity promoted aerosol heterogeneous chemistry, along with stagnant airflow and uninterrupted emissions from power plants and petrochemical facilities, contributing to severe haze formation. Also, because of nonlinear production chemistry and titration of ozone in winter, reduced nitrogen oxides resulted in ozone enhancement in urban areas, further increasing the atmospheric oxidizing capacity and facilitating secondary aerosol formation.

Surface Mapping of Earth-like Exoplanets using Single Point Light Curves.

Spatially resolving exoplanet features from single-point observations is essential for evaluating the potential habitability of exoplanets. The ultimate goal of this protocol is to determine whether these planetary worlds harbor geological features and/or climate systems. We present a method of extracting information from multi-wavelength single-point light curves and retrieving surface maps. It uses singular value decomposition (SVD) to separate sources that contribute to light curve variations and infer the existence of partially cloudy climate systems. Through analysis of the time series obtained from SVD, physical attributions of principal components (PCs) could be inferred without assumptions of any spectral properties. Combining with viewing geometry, it is feasible to reconstruct surface maps if one of the PCs are found to contain surface information. Degeneracy originated from convolution of the pixel geometry and spectrum information determines the quality of reconstructed surface maps, which requires the introduction of regularization. For the purpose of demonstrating the protocol, multi-wavelength light curves of Earth, which serves as a proxy exoplanet, are analyzed. Comparison between the results and the ground truth is presented to show the performance and limitation of the protocol. This work provides a benchmark for future generalization of exoplanet applications.

Ice nucleation by aerosols from anthropogenic pollution.

The formation of ice particles in the atmosphere strongly affects cloud properties and the climate. While mineral dust is known to be an effective ice nucleating particle, the role of aerosols from anthropogenic pollution in ice nucleation is still under debate. Here we probe the ice nucleation ability of different aerosol types by combining 11-year observations from multiple satellites and cloud-resolving model simulations. We find that, for strong convective systems, ice particle effective radius near cloud top decreases with increasing loading of polluted continental aerosols, because the ice formation is dominated by homogeneous freezing of cloud droplets that are smaller under more polluted conditions. In contrast, an increase in ice particle effective radius with polluted continental aerosols is found for moderate convection. Our model simulations suggest that this positive correlation is explained by enhanced heterogeneous ice nucleation and prolonged ice particle growth at larger aerosol loading, indicating that polluted continental aerosols contain a significant fraction of ice nucleating particles. Similar aerosol-ice relationships are observed for dust aerosols, further corroborating the ice nucleation ability of polluted continental aerosols. By catalyzing ice formation, aerosols from anthropogenic pollution could have profound impacts on cloud lifetime and radiative effect as well as precipitation efficiency.

Non-Monotonic Aerosol Effect on Precipitation in Convective Clouds over Tropical Oceans.

Aerosol effects on convective clouds and associated precipitation constitute an important open-ended question in climate research. Previous studies have linked an increase in aerosol concentration to a delay in the onset of rain, invigorated clouds and stronger rain rates. Here, using observational data, we show that the aerosol effect on convective clouds shifts from invigoration to suppression with increasing aerosol optical depth. We explain this shift in trend (using a cloud model) as the result of a competition between two types of microphysical processes: cloud-core-based invigorating processes vs. peripheral suppressive processes. We show that the aerosol optical depth value that marks the shift between invigoration and suppression depends on the environmental thermodynamic conditions. These findings can aid in better parameterizing aerosol effects in climate models for the prediction of climate trends.

Methane on Mars and Habitability: Challenges and Responses.

Recent measurements of methane (CH4) by the Mars Science Laboratory (MSL) now confront us with robust data that demand interpretation. Thus far, the MSL data have revealed a baseline level of CH4 (∼0.4 parts per billion by volume [ppbv]), with seasonal variations, as well as greatly enhanced spikes of CH4 with peak abundances of ∼7 ppbv. What do these CH4 revelations with drastically different abundances and temporal signatures represent in terms of interior geochemical processes, or is martian CH4 a biosignature? Discerning how CH4 generation occurs on Mars may shed light on the potential habitability of Mars. There is no evidence of life on the surface of Mars today, but microbes might reside beneath the surface. In this case, the carbon flux represented by CH4 would serve as a link between a putative subterranean biosphere on Mars and what we can measure above the surface. Alternatively, CH4 records modern geochemical activity. Here we ask the fundamental question: how active is Mars, geochemically and/or biologically? In this article, we examine geological, geochemical, and biogeochemical processes related to our overarching question. The martian atmosphere and surface are an overwhelmingly oxidizing environment, and life requires pairing of electron donors and electron acceptors, that is, redox gradients, as an essential source of energy. Therefore, a fundamental and critical question regarding the possibility of life on Mars is, "Where can we find redox gradients as energy sources for life on Mars?" Hence, regardless of the pathway that generates CH4 on Mars, the presence of CH4, a reduced species in an oxidant-rich environment, suggests the possibility of redox gradients supporting life and habitability on Mars. Recent missions such as ExoMars Trace Gas Orbiter may provide mapping of the global distribution of CH4. To discriminate between abiotic and biotic sources of CH4 on Mars, future studies should use a series of diagnostic geochemical analyses, preferably performed below the ground or at the ground/atmosphere interface, including measurements of CH4 isotopes, methane/ethane ratios, H2 gas concentration, and species such as acetic acid. Advances in the fields of Mars exploration and instrumentation will be driven, augmented, and supported by an improved understanding of atmospheric chemistry and dynamics, deep subsurface biogeochemistry, astrobiology, planetary geology, and geophysics. Future Mars exploration programs will have to expand the integration of complementary areas of expertise to generate synergistic and innovative ideas to realize breakthroughs in advancing our understanding of the potential of life and habitable conditions having existed on Mars. In this spirit, we conducted a set of interdisciplinary workshops. From this series has emerged a vision of technological, theoretical, and methodological innovations to explore the martian subsurface and to enhance spatial tracking of key volatiles, such as CH4.

Constraining Aging Processes of Black Carbon in the Community Atmosphere Model Using Environmental Chamber Measurements.

The direct radiative forcing of black carbon aerosol (BC) on the Earth system remains unsettled, largely due to the uncertainty with physical properties of BC throughout their lifecycle. Here we show that ambient chamber measurements of BC properties provide a novel constraint on the crude BC aging representation in climate models. Observational evidence for significant absorption enhancement of BC can be reproduced when the aging processes in the four-mode version of the Modal Aerosol Module (MAM4) aerosol scheme in the Community Atmosphere Model version 5 are calibrated by the recent in situ chamber measurements. An observation-based scaling method is developed in the aging timescale calculation to alleviate the influence of biases in the simulated model chemical composition. Model sensitivity simulations suggest that the different monolayer settings in the BC aging parameterization of MAM4 can cause as large as 26% and 24% differences in BC burden and radiative forcing, respectively. We also find that an increase in coating materials (e.g., sulfate and secondary organic aerosols) reduces BC lifetime by increasing the hygroscopicity of the mixture but enhances its absorption, resulting in a net increase in BC direct radiative forcing. Our results suggest that accurate simulations of BC aging processes as well as other aerosol species are equally important in reducing the uncertainty of BC forcing estimation.

Nitrogen Oxides in Early Earth's Atmosphere as Electron Acceptors for Life's Emergence.

We quantify the amount of nitrogen oxides (NOx) produced through lightning and photochemical processes in the Hadean atmosphere to be available in the Hadean ocean for the emergence of life. Atmospherically generated nitrate (NO3-) and nitrite (NO2-) are the most attractive high-potential electron acceptors for pulling and enabling crucial redox reactions of autotrophic metabolic pathways at submarine alkaline hydrothermal vents. The Hadean atmosphere, dominated by CO2 and N2, will produce nitric oxide (NO) when shocked by lightning. Photochemical reactions involving NO and H2O vapor will then produce acids such as HNO, HNO2, HNO3, and HO2NO2 that rain into the ocean. There, they dissociate into or react to form nitrate and nitrite. We present new calculations based on a novel combination of early-Earth global climate model and photochemical modeling, and we predict the flux of NOx to the Hadean ocean. In our 0.1-, 1-, and 10-bar pCO2 models, we calculate the NOx delivery to be 2.4 × 105, 6.5 × 108, and 1.9 × 108 molecules cm-2 s-1. After only tens of thousands to tens of millions of years, these NOx fluxes are expected to produce sufficient (micromolar) ocean concentrations of high-potential electron acceptors for the emergence of life. Key Words: Nitrogen oxides-Nitrate-Nitrite-Photochemistry-Lightning-Emergence of life. Astrobiology 17, 975-983.

Tightening of tropical ascent and high clouds key to precipitation change in a warmer climate.

The change of global-mean precipitation under global warming and interannual variability is predominantly controlled by the change of atmospheric longwave radiative cooling. Here we show that tightening of the ascending branch of the Hadley Circulation coupled with a decrease in tropical high cloud fraction is key in modulating precipitation response to surface warming. The magnitude of high cloud shrinkage is a primary contributor to the intermodel spread in the changes of tropical-mean outgoing longwave radiation (OLR) and global-mean precipitation per unit surface warming (dP/dTs) for both interannual variability and global warming. Compared to observations, most Coupled Model Inter-comparison Project Phase 5 models underestimate the rates of interannual tropical-mean dOLR/dTs and global-mean dP/dTs, consistent with the muted tropical high cloud shrinkage. We find that the five models that agree with the observation-based interannual dP/dTs all predict dP/dTs under global warming higher than the ensemble mean dP/dTs from the ∼20 models analysed in this study.

Hypotheses for Near-Surface Exchange of Methane on Mars.

UNLABELLED: The Curiosity rover recently detected a background of 0.7 ppb and spikes of 7 ppb of methane on Mars. This in situ measurement reorients our understanding of the martian environment and its potential for life, as the current theories do not entail any geological source or sink of methane that varies sub-annually. In particular, the 10-fold elevation during the southern winter indicates episodic sources of methane that are yet to be discovered. Here we suggest a near-surface reservoir could explain this variability. Using the temperature and humidity measurements from the rover, we find that perchlorate salts in the regolith deliquesce to form liquid solutions, and deliquescence progresses to deeper subsurface in the season of the methane spikes. We therefore formulate the following three testable hypotheses. The first scenario is that the regolith in Gale Crater adsorbs methane when dry and releases this methane to the atmosphere upon deliquescence. The adsorption energy needs to be 36 kJ mol(-1) to explain the magnitude of the methane spikes, higher than existing laboratory measurements. The second scenario is that microorganisms convert organic matter in the soil to methane when they are in liquid solutions. This scenario does not require regolith adsorption but entails extant life on Mars. The third scenario is that deep subsurface aquifers produce the bursts of methane. Continued in situ measurements of methane and water, as well as laboratory studies of adsorption and deliquescence, will test these hypotheses and inform the existence of the near-surface reservoir and its exchange with the atmosphere. KEY WORDS: Mars-Methane-Astrobiology-Regolith. Astrobiology 16, 539-550.